Dyestuffs of the anthraquinone series



UnitedStates Patent DYESTUFFS OF THE ANTHRAQUINONE SERIES Jakob Brassel, Basel, Alfred Fasciati, Bottmingen, and Arthur Bnehler, Rheinfelden, Switzerland, assignors to Ciba Limited, Basel, Switzerland, 2 Swiss firm No Drawing. Application August 13, 1954, Serial No. 449,782

Claims priority, application Switzerland August 20, 1953 9 Claims. (Cl. 260-249) This invention provides new dyestuffs which, like the product of the formula 0 NH ,NH-O c-Nn I l N SOaH correspond to the general formula (2) RX--B in which R represents the radical of an anthraqninone dyestufi, X represents a nitrogen bridge and B represents the radical of a heterocyclic compound having no dyestuif character, and which contains a single reactive halogen atom and no aromatically bound free amino or hydroxyl groups, and in which dyestuffs one of the radicals B and R, advantageously R, contains a sulfonic acid group.

This invention also includes a process for making the above dyestuffs, wherein an anthraquinone dyestufi which contains an amino group containing at least one reactive hydrogen atom and advantageously also contains a sulfonic acid group, is condensed with a heterocyclic dihalogen-compound containing a reactive halogen atom and which may contain as single ionogenic substit-uent a sulfonic acid group but no aromatically bound free amino or hydroxyl groups and has no dyestufi character, in such manner that the resulting dyestufi condensation product contains a single reactive halogen atom and advantageously a single sulfonic acid group.

As anthraquinone dyestuffs of the aforesaid kind there come into consideration as starting materials for the present process more especially those which contain a reactive NHz group in an external nucleus, that is to say, in a nucleus which is bound to the anthraquinone nucleus through an oxygen atom or advantageously through 2. NH group, such, for example, as aminobenzoylamino-anthraquinones or aminophenylamino-anthraquinones. Among these anthraquinone dyestuffs there are included above all dyestufis which contain an unchanged anthraquinone ring of the formula o o i can be used as starting materials for the present process, there may be mentioned? l;(-4-amiuobenzoylamino)-anthraquinoue, 1-,8-hydroxyethy1amino-4-(4'- or 3-aminohenylaminoyanthi'aquinone, l-methylamino-4-(4-aminophenylamino)-anthraquinone, and advantageously an- As examples of such anthraquinone dyestuffs, which a thraquinone dyestuffs containing sulfonic acid-groups,

2,773,871 Patented Dec. 11, 1956 ice pyrimidine and especially dihalogen-triazines of the formula (4) N\ AX-.-(iJ G-Halogen lilalogen in which A represents a hydrogen atom or a radical containing advantageously not more than 12 carbon atoms and which may contain as single ionogenic substituent a sulfonic acid group butno aromatically bound hydroxyl and amino groups and has no dyestufi character, and X represents an -S, O or -NH-- bridge.

The dihalogen-triazines of this constitution can be made by methods in themselves known from cyanuric halides such .as cyanuric bromide or cyanuric chloride, for example, by reacting 1 molecular proportion of cyanuric chloride with 1 molecular proportion of an amino-, mercaptoor hydroxy-compound having no dyestuti character, which is devoid of further aromatically bound free amino and hydroxyl groups. As such compounds there come into consideration, ammonia, aliphatic or aromatic hydroxyl compounds and mercaptans such as methyl alcohol, ethyl alcohol or butyl alcohol, phenol, ortho-, metaor para-cresol, 4-secondary butyl-phenol, 4-tertiary amylphenol, dialkyl-phenols, para-chlorophenol, fi-hydroxyethylmercaptan, dodecylmercaptan, thiophenol and especially organic nitrogen compounds such as methylamine,

dimethylamine, ethylamine, diethylamine, isopropylaminc,

=butylami ne, hexylamine, phenylamine, tolylamine, 4- chlorophenylamine, N-methyl-phenylamine or cyclohexylamine, and also fi-chloroethylamine, methoxyethylamine, ethanolamines, acetamide, butyric acid amide, urea, thiourea, toluene sulfonic acid amide, glycocoll, aminocarbonic acid esters such as the methyl or ethyl ester, ethylamino acetate, aminoacetamide, l-aminobenzene-Z- or 4-methyl sulfone, 1-aminobenzene-2-, 3- or 4-sultonic acid or their sulfonamides or sulfones. The primary condensation products so obtained still contain two reactive halogen atoms. Those which contain no sulfonic acid groups are to be condensed only with anthraquinone dyestuifs of the kind described above which contain sulfonic acid groups.

The condensation of the aforesaid heterocyclic dihalogen-compounds with the anthraquinone dyestuffs is advan- Iageously carried out in the presence of an acid-binding agent, such as sodium acetate or sodium carbonate, and ,under conditions such .that the final product still contains an exchangeable halogen atom, that is to say, for example, in an organic solvent or at a relatively low tempera ture intan aqueous medium.

The especially valuable dyestufis of the Formula 2 3 which contain a triazine residue, can also be made by a modification of the process described above. This modified process consists in condensing an anthraquinone dyestufi which contains an NH2 group and advantapended in 50 parts of acetone and 300 parts of water, and then 51.1 parts of the monosodium salt of l-amino- 4- (4'-aminophenylamino)-anthraquinone-2:3' disulfonic acid are added. After the addition of 50 parts by volume geously also a sulfonic acid group with a cyanuric halide, 5 of a 4-molar solution of sodium acetate, the mixture is especially cyanuric chloride, in the molecular ratio of heated under reflux, while stirring, at 45-50 C., the 1:1 and, in the resulting condensation product which conprecipitated dyestufl is filtered off and washed with sodium tains two exchangeable halogen atoms reacting a further chloride solution of 1 percent strength. The filter cake halogen atom with a hydroxy-, mercaptoor amino-comso obtained is dried in vacuo at about 50? C. The resultpound having no dyestuff character, and which is free ing dyestuff after being ground is a darkblue powder. from further aromatically bound hydroxyl and amino It dissolves in water with a blue coloration and dyes wool groups. from weakly acid baths blue tints which are fast to wash- As hydroxy-, mercaptoor amino-compounds having ing and fulling. no dyestufi character, and which are free from further 1 aromatically bound hydroxyl and amino groups, there Examlle"2 come into consideration those which are mentioned above I I i Y for making the dihalogen-triazines. As anthraquinone pafts of the Salt of f dyestufis there likewise come intoconsideration those phenylammi?)'anthrifqumone'z'sulfomc? acld mentioned above, and the preparation andworking up pended or dissolved'm about 1900 parts of water, and 18 of the ,dyestuft' condensation products is also carried out 20 Parts the p ry Condensation product from 1 mol of in such manner that the isolated product contains a reacchlonde and 1 f ammoma are added- The tive halogen atom, that is to say, in an aqueous medium Whole surfed a long [Elma at abPut 30-35? and at as low a temperature as Possible, and n the presence the ac1d which is liberated 1s neutrallzed by the gradual of an acid-binding agent or if desired in an organic solvent. addltlon P 5 Parts of e carbonate- The fly The new products of this invention are valuable dyer d 1S Completely precipitated by the addition of stuffs which are suitable for dyeing or printing a very sofhum m T dyestuf? is filtereq Ofi i wide variety of materials, especially nitrogenous textile Wlth m 5011mm chlonde and -P m materials such as silk, leatherand abovg an W001, and my vacuo. The isolated dyestufi isablue powder WhlCh disalso synthetic fib f superpolyamides or superpobh solves in water with' a blue'coloration, and dyes wool urethanes. In addition to being suitable for normal acid and fibers of uperpolyam1des from weakly acld baths dyeing, for example, from baths containing sulfuric acid, greemsh blu e tmts which are fast to wahing-I they are also especially suitable for dyeing fromweakly By Instead of 18 Parts of f condensa alkaline, neutral or weakly acid baths, advantageously Pmdufit from 1.11101 of cyanunc chlonde and 1 mol from baths having a pH value between 5 and 7. The dyeof amIPOma, a sohmon of 7 Parts of f Pri ary conings and prints so produced are distinguished by {h densation product from 1 mol of cyanuric chloride and 1 Special purity f their tints, by a good f t to light mol of aniline m 100 parts of tetrahydrofurane, there is and by an excellent fastness to washing and fulling, espe- Obtained a 'dyestufi which is Somewhat more p ly ciallyin the alkaline region, soluble in water, and which dyes wool fromrweakly acid The following examples illustrate the invention, the or neutral baths greenish blue tints'of good fastness to parts and percentages being by weight unless otherwise 40 washing or fulling. stated and the relationship of parts by Weight to parts By using instead of the anthraquinone dyestufi meny Volume belng the Same as that Of the kllogl'am t0 the tioned above, those given in column I of the following liter: table, and, instead of the aforesaid condensation product, a 1 p 1 m the primary condensation products given in column H, 24,1 parts f th primary d ti product f there are obtained dyestufis which dye wool the tints given 1 mol of cyanuric chloride and 1 mol of aniline are susin column III: a

I II III Primary condensation product Anthraqumone dyestufi from 1 mol oficyanurie chlo- Dyelng on wool ride and 1 mol ot 1 808E aniline.-- reddishblue.

NH: 00 I 2 :11 phenol -Q NH-OHaCHsOH 7 C0 3 l-amlnobenzene-a-sultonio aeid.- green-blue.

I II III Primary condensation product Anthmquinone dyestufi from 1 mol of cyanuric chlo- Dyeing on wool ride and 1 mol of- NH: 00 i 4 O: -s 03H methylamine blue.

NH: 00 I 5 0 S 0311 chloracetamide greenish blue.

NH: 00 l s O: s 0312! eyclohexylamine blue.

NH: 00 I 1 O: som o-chloraniline Do.

NH; 00 l 8..-..- Q S 03H m-chloraniline Do.

NE NE:

NH: c0 1 9...... O: SOzH p-chloraniline Do.

NH NE:

NH: 00 z 10-..; [1 -s0a1 o-methylaniline Do.

NH: 00 i 11"-.. S 0 H o-methoxyaniline Do.

NH NH:

I II III Primary condensation product Anthraquinone dyestufi y from 1 mol of cyanuric chlo- Dyeing on wool ride and 1 mol of- NH: 0 0 I 12. O s 03H 2-methy1-6-ch1orani1ine blue.

NH: 0 0 1 13..- 'S 03H 1-aminobenzene-4-methy1 5111- Do.

I tone.

C O I NH 4 0 0 l V 14 a S 0:13 benzylamine Do.

00 I I G NH: c 0 l V15..- S 95H benzene sulfonic acid amide"... Do.

NH: 0 o 16----- Oi s OaH a-furylmethylalmne D0.

C O 17..-" 0 S OaH morpholjpe Do.

O 0 18..-" a S 01H dimethylamine Do.

NH: I c o 19---- 5 0,11 N-methylaniline Do.

I II III Primary condensation'product Anthraqninone dyestufl' from 1 mol of cya'nurle 'ehlo- Dyaing-onwool ride and 1 mol oI- NH: 00 I 2'0"--- O SOQH n-dodecyl mercaptan. blue.

NH NH:

O O 21..-.. S 03H fl-hydroxyethyl mercaptan Do.

NH: 00 I 22..--- S 03H phenol reddish blus- NH: 00 23... som aniline blu'e.

NH: 00 I '24..-" SOsH n-dodeeyl mercaptan. Do.

NE NH:

NH7 0 0 25.---- SO3H B-hydroxyethyl mercaptan.--.. Do.

NH: 0 o 2s..... S0311 aniline t'eddish blue.

NHI 00 I 27..- phenol Do.

1 1 Example 3 43.1 parts ofthesodium salt of 1-amin0-4-(4'-aminophenylamino)-anthraquinone-2-sulfonic' acid are dissolved in about 1000 parts of water with the addition of 4.4 parts ofcaustic soda and 7 parts of sodium carbonate, and 14.9 parts of 2:4-dichloropyrimidine are added. The mixture is stirred at about 3550 C. until the condensation is finished, and thedyestufl? formed is precipitated by the addition of sodium chloride. After filtering oflE and washing the dyestufi with dilute sodium chloride solution, it is dried in vacuo. The dyestufi isolated in this manner is a blue powder which dissolves in water and dyes wool and superpolyamide fibers from weakly acid baths full greenish blue tints.

By using, insteadof the aforesaid anthraqninone de rivative, 5.4 parts 'of the l-amino-4-(4'-aminophenylamino)-anthraquinone-3'-sulfonic acid diethylamide-Z- sulfonic acid of the formula NH: O

NH O Q Whm and otherwise proceeding in the same manner, there is obtained a very similar dyestufi, which dyes wool from weakly acid or neutral baths also greenish blue tints.

Example 4 43.1 parts of the sodium salt .of 1-amino-4-(4-aminophenylamino)-anthraquinone-2-sulfonic acid are dissolved in about 1000 parts of water with the addition of 4.4

parts of caustic soda and 7 parts of sodium carbonate and 19.9 parts of 2:4-dichloroquinazoline are added. The whole is stirred for a long time at about 40 C. until the condensation is finished, and the dystesuff formed is precipitated by the addition of sodium chloride. After filtering ofi the dyestuif and washing it with a dilute solution'of sodium chloride, it is dried in vacuo. The dyestufi so isolated is a blue powder which dissolves in water and dyes wool and superpolyamide fibers from weakly acid baths full greenish blue tints.

A blue dyestufl? is obtained by using l-amino-4-(4- amino 3 methylphenylamino) anthraquinone 2- sulfonic acid, instead of the anthraquinone derivative described above.

Example 5 2 parts of the dyestufi obtained as described in Example 1 are dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added to the resulting dyebath, and 100 parts of wool are entered at 40-50" C.

2 parts of acetic acid of 40 percent strength are then added, the bath is raised to the boil in the course of /2 hour, and dyeing is carried on for hour at that tempera ture. After rinsing and drying the material, there is obtained a greenish blue dyeing which is fast to light, and has a very good fastness to washing and fulling.

The same result is obtained by using, instead of wool, I

Y in'which R2 represents a benzene radical, Z represents a member of the group consisting'of a sulfonic acid group and a hydrogen atom, A represents a member of the group consisting of benzene cyclohexyl and alkyl radicals of at most 12 carbonatoms and X represents a member of the group consisting of, an oxygen atom and an -NH group, one of the radicals R2 and A containing as sole Water-solubilizing substituent a sulfonic acid group when Z represents a hydrogen atom.

2. An ,anthraquinone dyestuif of the formula in which R2 represents a benzene radical, one of the two Zs represents a sulfonic acid group and the other a hydrogen atom and A represents a hydrocarbon radical of at most 12 carbon atoms.

3. An anthraquinone dyestufl of the formula in which-Rs represents a benzene radical, one of the two Zs represents a sulfonic acid group and the other a hydrogen, atom and A represents a benzene radical free from water-solubilizing substituents.

4. An anthraquinone dyestuif of the formula .wherein n represents awhole number up to 2 and A represents a six-membered carbocyclic ring free from water-solubilizing substituents.

-5. The anthraquinone dyestufi of the formula 00 I 40,11 01 O I I A c6 fI I 6. The anthraquinone dyestufi of the formula 7. The anthraquinone dyestufi of the formula 9. The anthraquinone dyestufi of the formula NE: NH: c1

8. The an'thraquinone dyestulf of the formula OH:

NH: References Cited in the file of this patent 00 1 UNITED STATES PATENTS f 15 2,235,480 Graenacher Mar. 11, 1941 K 0H1 FOREIGN PATENTS 00 97,360 Switzerland 1923 if NH NHC c-NH 

1. AN ANTHRAQUINONE DYESTUFF OF THE FORMULA 